EP2820702A2 - Construction améliorée d'un accumulateur au plomb-acide - Google Patents

Construction améliorée d'un accumulateur au plomb-acide

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Publication number
EP2820702A2
EP2820702A2 EP13757746.6A EP13757746A EP2820702A2 EP 2820702 A2 EP2820702 A2 EP 2820702A2 EP 13757746 A EP13757746 A EP 13757746A EP 2820702 A2 EP2820702 A2 EP 2820702A2
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EP
European Patent Office
Prior art keywords
lead
electrode
cell according
acid battery
conductive
Prior art date
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EP13757746.6A
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German (de)
English (en)
Other versions
EP2820702B1 (fr
EP2820702A4 (fr
Inventor
Shane CHRISTIE
Yoon San WONG
Grigory Titelman
John Abrahamson
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Arcactive Ltd
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Arcactive Ltd
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Priority to EP18161167.4A priority Critical patent/EP3367482B1/fr
Publication of EP2820702A2 publication Critical patent/EP2820702A2/fr
Publication of EP2820702A4 publication Critical patent/EP2820702A4/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/627—Expanders for lead-acid accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to an improved battery construction for lead-acid batteries particularly but not exclusively automotive batteries for hybrid vehicles.
  • a Pb-acid battery stores and releases energy by electrochemical reaction(s) at the surfaces of its electrodes.
  • Each cell in the fully charged state contains electrodes of elemental lead (Pb) and lead (IV) dioxide (PbO,) in an electrolyte of dilute sulfuric acid (H 2 S0 4 ).
  • PbS0 4 lead(II) sulfate
  • the electrolyte loses its dissolved sulfuric acid and becomes primarily water.
  • each plate consists of a lead grid initially filled with a paste comprising a mixture of leady oxide (Pb and PbO) and dilute sulfuric acid.
  • the paste may also contain carbon black, blanc fixe (fine barium sulfate), and lignosulfonate.
  • vehicle batteries which are most commonly Pb-acid batteries.
  • European Union has set a long-term emissions target of not more than 95 g carbon dioxide/km to be reached by 2020 for new vehicles.
  • DCA dynamic charge acceptance
  • Vehicles with a higher level of hybridisation including vehicles comprising both an internal combustion engine and an electric motor typically comprise regenerative braking, in which braking force is applied by a generator the electric energy from which is stored in the vehicle battery.
  • the vehicle battery is charged only by current from regenerative braking during time periods in which the internal combustion engine which also drives a generator (which here includes alternator) is not operating.
  • regenerative braking relatively high charging currents are supplied to the vehicle battery for short time periods and thus batteries for hybrid vehicles with regenerative braking should also have high DCA.
  • Full electric vehicles also comprise regenerative braking.
  • the charging system of a hybrid vehicle is arranged to use the engine-driven generator to maintain the charge state of the vehicle batter)' at less than full charge such as for example at about 80% charge, so that there is generally capacity available to accept additional charging energy from regenerative braking.
  • the battery DCA then typically declines over time with increasing number of discharge and charge (to less than full charge) cycles, with AGM batteries typically operating at around 0.1 to 0.3 A/Ah (or 0.1 to 0.3C) within a few thousand cycles. This loss in charge acceptance reduces the fuel saving capability of the vehicle;
  • the charging system of a hybrid vehicle is arranged to allow the battery to discharge and then (using the engine-driven generator to) charge the battery.
  • the cars Battery Management System will periodically fully charge die battery (or "recondition" the battery) to restore the battery DCA, such as every three months.
  • An ideal Pb-acid battery, particularly for a hybrid vehicle would maintain DCA without requiring periodic full charging, or at least would maintain a higher rate of DCA between reconditioning cycles.
  • a battery should also meet other requirements, such as have high volumetric energy density.
  • Volumetric energy density refers to the energy supplied per unit volume of electrode.
  • a closed Pb-acid battery system should also have low water consumption.
  • an automotive battery in particular should be able to deliver high current for engine starting, at low temperature.
  • a cold cranking amps (CCA) test tests the ability of a battery to do so.
  • US patent No. 7569514 describes utilising activated carbon as an electrode in an absorbed glass mat battery to overcome sulphation to thereby increase the dynamic charge acceptance of the battery.
  • US patent No. 4429442 describes a lead-acid battery plate comprising a metal grid and active mass and a layer of carbon fibrous material on the side of the active mass to enhance mechanical integrity of the active mass.
  • US patent No.4342343 describes a negative lead-acid storage battery plate with interconnected carbon fibres over the face of a pasted plate. During manufacture formability is enhanced by securing the fibres to a paper carrier and then pressing the same to the plate.
  • US patent No. 6617071 describes an electrode having a conductive polymeric matrix formed over the surface of a grid plate where the conductive polymeric matrix comprises superfine or nanoscale particles of active material.
  • WO2011/078707 discloses a lead-acid battery comprising as a current collector a conductive fibrous material of filaments with low interfibre spacing and conducting chains of Pb-based particles attached to the fibres, which provides improved batter)' performance particularly DCA.
  • the invention comprises a lead-acid battery or cell including at least one (non-composite or composite) electrode comprising as a current collector a conductive fibrous material comprising, when fully charged, voidage (being the fractional volume occupied by the pores between the lead and conductive fibres) of between about at least about 0.3, and a mass loading ratio of lead (in whatever form) to the mass of conductive fibres, when converted to volume ratio, in the range about 0.7:1 or about 1 :1 to about 15:1 or about 10:1 (each over at least a major fraction of the electrode and more preferably over substantially all of the electrode).
  • voidage being the fractional volume occupied by the pores between the lead and conductive fibres
  • mass loading ratio of lead in whatever form
  • the invention comprises a method for manufacturing a lead-acid battery or cell which includes forming at least one (non-composite or composite) electrode comprising as current collector a conductive fibrous material comprising when fully charged, voidage (being the fractional volume occupied by the pores between the lead and conductive fibres) of at least about 0.3, and, a mass loading ratio of lead to the mass of conductive fibres, when converted to volume ratio in the range about 0.7:1 or about 1:1 to about 15:1 or about 10:1.
  • the voidage is between about 0.3 and about 0.9, about 0.3 and about 0.85, more preferably between about 0.3 and about 0.8, more preferably between about 0.5 and about 0.98, further preferably between about 0.8 and about 0.95.
  • die volume loading ratio of the active material when converted to Pb to conductive fibres is between about 0.7 :1 or about 1:1 and about 7:1, or about 1.5:1 and about 5:1, or about 2:1 and about 4:1.
  • the voidage may be present as corridors to form between die lead and carbon to enable lead particles to form between each of the carbon fibres.
  • the average spacing between conductive fibres is between about 0.5 and about 10, more preferably between about 1 and about 5 fibre diameters.
  • the average interfibre spacing between fibres is less than 50 microns or less than 20 microns.
  • said average interfibre spacing is over at least a major fraction of the material and more preferably over substantially all of die material.
  • the average fibre diameter is less than about 20 or less than about 10 microns.
  • the invention comprises a lead-acid battery or cell including at least one (non-composite or composite) electrode comprising as a current collector a conductive fibre material comprising, when fully charged, voidage (being the fractional volume occupied by the pores between the lead and conductive fibres) of at least about 0.3 and a loading ratio of the volume of lead (in whatever form) to the volume of conductive fibres (each over at least a major fraction of the electrode) which together define a point on a plot of voidage (x axis) versus loading ratio of the volume of lead to the volume of conductive fibres (y axis) that falls within an area defined by one line on said plot from an x axis voidage value of about 98% with a slope of about -1/0.02 and the another line on said plot an x axis voidage value of about 70% with a slope of about -1/0.3.
  • voidage being the fractional volume occupied by the pores between the lead and conductive fibres
  • the voidage and mass loading ratio of lead to the mass of conductive fibres when converted to volume ratio together define a point on said plot that falls within an area defined by one line from an x axis voidage value of about 97% with a slope of about -1/0.03 and another line from an x axis voidage value of about 80% with a slope of about -1/0.2, or an area defined by one line from an x axis voidage value of 96% with a slope of - 1/0.04 and another line from an x axis voidage value of 85% with a slope of about -1/0.15.
  • the invention comprises a lead-acid battery or cell including at least one (non-composite or composite electrode comprising as a current collector a carbon fibre material having a carbon fibre volume fraction of less than 40%, and a loading ratio of the volume of lead (in whatever form) to the volume of carbon fibres greater than 0.5 (each over at least a major fraction of the electrode and more preferably over substantially all of the electrode).
  • the carbon fibre volume fraction of less than 30%, and mass loading ratio of lead to carbon fibres converted to volume ratio is greater than 0.7, or the carbon fibre volume fraction is less than 20% and mass loading ratio of lead to carbon fibres converted to volume ratio is greater than 1:1.
  • d e invention comprises a lead-acid battery or cell including at least one (composite) electrode comprising as a current collector a conductive fibrous material, and comprising a metal grid, the electrode also comprising a current generating electrolyte active mass at least 20% of which is in the conductive fibrous material.
  • At least 40%, 50%, 80%, or not more than 80% of the active mass is in the conductive fibrous material.
  • less than 80%, 60%, 50%, or 20% of the active mass may be dispersed in the metal grid.
  • conductive fibrous material comprises a carbon fibre material and the metal grid comprises a lead grid.
  • the conductive fibrous material is present as multiple layers at least one on either side of the metal grid.
  • the conductive fibrous material is present as a single layer on one side of the metal grid.
  • the metal grid may have a similar superficial surface area or be of similar height and width dimensions particularly in a major plane, to the conductive fibrous material element(s) but in alternative embodiments the metal grid may have smaller dimensions for example of smaller height and width dimensions, and may comprise for example a narrower lead strip between two larger carbon fibre layers on either side thereof.
  • the carbon fibre layer(s) are conductively connected to the metal grid so that the grid receives current from the carbon fibre layer(s) and connects the electrode externally thereof.
  • the conductive fibrous material may be a woven material (comprising intersecting warp and weft fibres), a knitted material, or a non- oven material such as a felt material.
  • the positive electrode or electrodes, the negative electrode or electrodes, or both, may be formed of one or more layers of the conductive fibrous material.
  • Preferably the conductive fibrous material density is also lighter than that of lead.
  • the current collector material may comprise a carbon fibre material such as a woven or knitted or felted or non-woven carbon fibre fabric. Carbon fibre current collector material may be heat treated to sufficient temperature to increase its electrical conductivity. The thermal treatment may be by electric arc discharge.
  • the conductive fibrous material has length and width dimensions in a major plane of the material and depth perpendicular to said major plane of the material.
  • the current collector fibrous material may have an average depth of the material of at least 0.2mm or at least 1mm and/ or less than 5 mm or 3 mm or 2mm.
  • the current collector may comprise multiple layers of the conductive fibrous material.
  • the current collector material has bulk resistivity less than 10 ⁇ mm and preferably less than 1 ⁇ mm or 0.1 ⁇ mm.
  • the invention comprises a lead-acid batter ⁇ ' or cell including at least one electrode comprising as a current collector a conductive fibrous material, and comprising a metal grid, the electrode also comprising a current generating electrolyte active mass, the conductive fibrous material having a bulk resistivity of less than 10 ⁇ mm.
  • cells and/ or batteries comprising an electrode construction of the invention may have both improved or relatively high DCA and CCA, and/or may maintain DCA or a higher rate of DCA with an increasing number of charge-discharge cycles, and thus may be particularly suitable for use in hybrid vehicles.
  • Cells and/ or batteries of the same or other embodiments of the invention may also or alternatively have reduced water consumption and/or improved or relatively high VED and/or improved battery life.
  • the term "comprising” as used in this specification means “consisting at least in part of. When interpreting each statement in this specification that includes the term “comprising”, features other than that or those prefaced by the term may also be present. Related terms such as “comprise” and “comprises” are to be interpreted in the same manner.
  • Figure 1 is a plot of ratio of active material to carbon (volumetric ratio) versus voidage, for various negative electrodes used in a lead acid cell, all made up from active material loaded into a carbon matrix,
  • Figure 2 is a plot of areas of ratio of active material to carbon (volumetric ratio) versus voidage, that also includes the various electrodes in Figure 1 ,
  • Figure 3a schematically shows a carbon fibre electrode with a metal lug for external connection of the electrode formed on the carbon fibre material by pressure die casting
  • Figure 3b shows a different shaped lug with a tab addition
  • Figure 3c shows a cross-section of multiple layers of carbon fibre material with a lug
  • Figure 4 schematically shows an electrode of an embodiment of the invention from one side with a metal wire or tape attached to one side as a macro-scale current collector
  • Figure 5 is a schematic cross-section through an electrode of an embodiment of the invention with a metal wire or tape attached to one side as a macro-scale current collector,
  • Figure 6 is a schematic cross-section through an electrode composed of two sections of electrode material of an embodiment of the invention with a metal wire or tape embedded or sandwiched between as a macro-scale current collector,
  • Figure 7 is a schematic cross-section view of illustrating felt splitting for forming carbon fibre electrode material of some embodiments of the invention.
  • Figure 8 schematically illustrates one form of reactor for the continuous or semi- continuous activation of a carbon fibre material for use as a current collector material according to the invention
  • Figure 9 is a close up schematic view of the electrodes and the material path between the electrodes of the reactor of Figure 8,
  • Figure 10 shows a DCA test algorithm referred to in the subsequent description of experimental work
  • Figure 11 shows the High Rate DCA performance of two composite electrodes N359 and 371 referred to in the subsequent description of experimental work
  • Figure 12 shows the CCA performance of electrode N349 referred to in the subsequent description of experimental work, as tested using SAE J537 at a high rate of 310 mA/square cm of electrode surface area facing another electrode
  • Figure 13 shows the current versus charging overpotential (Tafel Line) of electrode 411 referred to in the subsequent description of experimental work, as compared to a traditional electrode, demonstrating similar water consumption properties
  • Figure 14 shows the current versus charging overpotential (Tafel Line) of electrode 305 referred to in the subsequent description of experimental work, but is shows less desirable water consumption properties than a traditional electrode,
  • Figure 15 shows the High Rate DCA performance of electrode 409, a 60mm long electrode with a wire current collector, referred to in the subsequent description of experimental work, which demonstrates good DCA performance compared to a traditional electrode,
  • Figure 16 shows the High Rate DCA performance of electrode 356 while 60mm long, with no wire current collector, referred to in the subsequent description of experimental work, which has DCA performance less than an electrode with a wire current collector, but still better than a traditional electrode,
  • Figure 17 shows the High Rate DCA performance for elecUode 356 referred to in the subsequent description of experimental work, after the initial 35,000 cycles (shown in Figure 16) and reduced in length to 30mm, and then tested at the same charging current density as before, and shows exceptional DCA performance, and
  • Figure 18 shows the DCA performance of electrode 410 when using the Axion DCA test, as compared to the typical DCA performance of a traditional lead acid Battery.
  • a lead-acid battery or cell includes at least one electrode comprising as a current collector a conductive fibrous material comprising voidage (being the fractional volume occupied by the pores between the lead and conductive fibres) when fully charged of at least about 0.3, and a mass loading ratio of lead (in whatever form) to the mass of conductive fibres, when converted to volume ratio in the range about 0.7:1 or about 1:1 to about 15:1 or about 10:1. (and assuming full conversion of all active material to Pb when fully charged).
  • the voidage is between about 0.3 and 0.9, between about 0.3 and about 0.85, between about 0.3 and about 0.80, between about 0.5 and about 0.98, between about 0.7 and 0.95, between about 0.5 and 0.98, or between about 0.8 and about 0.95, and the volume loading ratio of the active material when converted to Pb to conductive fibres is between about 0.7 :1 or about 1:1 and about 7:1, between about 1.5:1 and about 5:1, or between about 2:1 and about 3:1.
  • the ratio of active material volume to carbon volume refers to the volume of the Pb- containing active material in the conductive fibrous matrix.
  • Voidage refers to the void volume among the particles of active material and the conductive fibrous matrix, divided by the total volume.
  • Figure 1 allows for different matrix voidages, variation of the extent of filling this matrix voidage with solid active material for example at pasting, and variation in state of charge.
  • Each line is drawn between the volume ratio and voidage for two extreme forms of die active material contained in a given carbon matrix. For most electrochemical cycling these two forms are Pb and PbS0 4 .
  • Electrodes made with a specific carbon matrix occupy a single line on the chart, and pass through the point of matrix voidage with no active material.
  • the extent of active material loading (and the form it is in e.g.
  • PbS04, or Pb determines which point on the (straight) line the electrode is (currendy) represented by, taking account of the different densities of the different forms, and how much of each is present. For example, if the matrix is initially loaded with PbS0 4 , and then fully charged to Pb, this formation is represented by travelling along a section of the line, "fully discharged” to "fully charged”. If the matrix is initially loaded with PbO and then fully charged to convert this to Pb, then a different line is drawn to represent the path from PbO to Pb. However after this first conversion to Pb, the path followed in any subsequent cycling will follow the line between Pb and PbS0 4 .
  • discharge/ charge from this full charge point on will be represented by paths along the same line as when initially loaded with PbS0 4 . Only when it is fully charged (i.e., at 100% Pb) will the electrode using PbO as the precursor be represented on the more useful PbS04/Pb line and thereafter i.e. during further cycles, the electrode path will be on that line.
  • the lines labelled 349, 363, and 441 in Figure 1 are for electrodes the construction of which is described in the subsequent experimental examples. The lowermost points of each line represents the conditions where all the loaded active material has been converted to Pb.
  • the voidage within the electrodes of a lead-acid cell or batter ⁇ ' is important for both containing one of the active materials— the acid— and for allowing ions access to the surface that supplies or accepts electrons.
  • This volume as the fraction of the total volume ('voidage') of the part of the electrode containing the electrolyte.
  • the ratio of volume of lead to volume of conductive fibre such as carbon fibre refers to the balance between the matter (Pb) potentially capable of yielding charge or accepting it, and the matter of conductive fibre such as carbon fibre providing a conduit for the electrons and optionally also a catalytic surface for the electrochemical reactions. This ratio may be expressed as a volume ratio.
  • Both volume and mass ratios can be calculated for the fully charged state (where only Pb exists) and fully discharged state (only PbS0 4 ). In normal cycling charge and discharge, die discharge finishes before reacting 100% of the PbS0 4 .
  • Any given electrode can be characterised by two parameters: 1. the matrix voidage before loading with active material (or more convenientiy the matrix volume fraction which is 1 minus this voidage), and 2. the volume ratio of the active material and carbon matrix when the active material has been fully converted to lead.
  • a further parameter can be represented on the chart.
  • the utilization of lead to provide charge is the fraction of the total possible path travelled from Pb to PbS0 4 that the electrode is capable of during discharge.
  • the volume ratio that is of importance for reaction rates is the voidage of the electrode material and lead-containing particles. This voidage is needed to allow the ions of acid and Pb++ to diffuse to and from the reacting surface.
  • Pb and PbS0 4 particles after many cycles This small particle size gives a sufficient surface area for sufficient dissolution of PbS0 4 or Pb into Pb++ to give the rates and currents required, when the particles are close to a carbon fibre surface, which catalyses the current creation reactions.
  • the size of the particles after many cycles may be closely related to the size of the interfibre spacing between the conductive fibres, so that the particles fit between them. Thus with smaller diameter conductive fibres at the same total volume fibre fraction the gaps between these will be proportionately smaller and also the active particles will be proportionately smaller. Thus higher surface areas and higher rates may be achieved with smaller fibres.
  • the conductive fibrous material comprises filaments of average length in the range 3 to 50 mm.
  • substantially all or at least a majority of filaments/ fibres of the electrode material extend continuously across the electrode between or to a metal frame or frame elements to which both ends or at least one end of the fibres is/are electrically connected.
  • a woven fabric of continuous fibres may be optimal.
  • Example 1 composite electrode of carbon fibre paper with Pb grid - N371
  • An electrode was constructed from carbon fibrous paper carbon mat (Z-Mat produced by Zoltek) of thickness of 3 mm, ⁇ 6 % carbon fraction in volume, specific weight ⁇ 312 g/m 2 , and fibre length of 25 mm. Two pieces were cut to dimensions 44 mm*70 mm and then split into thinner layers to produce individual layers of average thickness of 0.26mm. The electrode was constructed by placing one of these carbon fibrous layers on each of the two surfaces of a lead grid.
  • Z-Mat produced by Zoltek
  • Paste was prepared starting with 19.5 g of leady oxide (leady oxide batch purchased from Exide in 2009) to the same composition as set out in examples 1 and 2 above and followed the same mixing procedure in the ultrasound bath under same conditions.
  • the carbon felt piece was placed on the plate which used for pasting.
  • the above prepared paste was spread on the felt layer until a smooth distribution of paste on the surface was obtained.
  • the felt piece was then placed on the ultra-sound vibration plate so that the un-pasted surface faced up and paste was distributed on this surface using a flexible plastic spatula. Ultrasound vibration was on for ⁇ 50 sec during pasting.
  • Example 4 non-composite electrode of arc treated carbon felt, active mass/ carbon volume ratio ⁇ 4.52 - N439 - see figure 12
  • An electrode was constructed of carbon fibrous layers of arc-treated carbon felt (Sigracell KFD2.5 EA) manufactured by SGL Carbon Company, Germany).
  • the felt was treated in an electric arc generally as previously described with reference to Figures 7 and 8.
  • the felt before arc-treatment had a specific weight of 248 g/m 2 , thickness of 2.6 mm, and carbon volume fraction ⁇ 6 %.
  • the material post arc- treatment had 197 g/m 2 specific weight, was 2.33 mm thick, and had ⁇ 6 % carbon volume fraction.
  • Lead coated Cu wires 0.38 mm in diameter were used as an additional current collector for the above electrode. These were laid on the felt surface manually along the length of the felt in a zig- zag manner with the vertical strips evenly spaced along the width, prior to injecting the lug. The lug was injected onto the felt so that the top of each zag of the Cu wire was immersed in the lug and attached to the lug.
  • Paste was ptepated with 23 g of leady oxide (leady oxide batch purchased from Exide in 2009) , 1.5 g of diluted sulphuric acid, 0.023 g of Vanisperse A (expander) to achieve 0.1% expander in the paste and 0.184g of barium sulphate.
  • the same mixing procedure was followed for paste preparation and pasting as explained in previous examples of N363 and N364.
  • Ultrasound vibration was on for ⁇ 1.30 min during pasting. (Ultra-sound vibrating plate manufactured by Skymen Cleaning Equipment Shenzhen Co. Ltd was used, current rating on the US plate used was 1.75A, and the electrode was placed covering one transducer point on the plate). The pasted electrode was turned over a couple of times while die ultra-sound was in operation until a smooth distribution of paste on the surface was observed where the majority of paste had penetrated to the felt.
  • the total amount of wet mass loaded into the electrode was 24. 62 g where the achieved capacity (low current discharging) was 3.077 Ah (i.e. 62% of the theoretical capacity).
  • the pasted electrode active area (pasted) dimensions were, length 59 mm, width 45 mm, and thickness 2.7 mm.
  • the achieved lead loading per volume was 2.63 g/ cm .
  • active mass Pb to carbon volume ratio is 4.52.
  • the average spacing between carbon fibres was about 40 microns.
  • Subsequendy the electrode was air-dried for 24 hours at ambient temperature ( 8 "C— 24 n C) and then the pasted electrode was assembled in a cell containing electrolyte of 1.15 sg H 2 S0 4 with one (40% SOC) positive electrode on each side. The cell was left soaking for 24 hours at ambient temperature (18 "C - 24 “C). Then formation charging and stabilisation was carried out similarly as for example 1.
  • Lead coated Cu wires of 0.38 mm in diameter were used as an additional current collector for the above electrode. These were laid on the felt surface manually along the length of the felt in a zigzag manner where the vertical strips were evenly spaced along the width.
  • the total amount of wet mass loaded in to the electrode was 17.08 g where the achieved capacity (low current discharging) was 2.15 Ah (i.e. 67.7% of the theoretical capacity).
  • the pasted electrode active area (pasted) dimensions were, length 60.5 mm, width 44.1 mm, and thickness 3.6 mm.
  • the achieved lead loading per volume was 1.28 g/cm 3 .
  • active mass Pb to carbon volume ratio is 3.63.
  • the average spacing between carbon fibres was about 40 microns.
  • PbS0 4 powder (mean size 4-5 ⁇ after milling) was mixed in with low concentration sulphuric acid (s.g. ⁇ 1.05) to make a paste of 77.3 mass % PbS0 4 .
  • the above lug was placed on a flat plate.
  • the lug was placed on the pasting plate holding the top three layers up from the plate while the fourth lay flat on the plate.
  • Paste was applied on the fourth layer on the flat plate.
  • the next layer was then released onto the first layer.
  • Paste was distributed on the surface of the second layer until achieving a smooth surface.
  • the above procedure was repeated for the next two layers. Then the whole construction was turned over on the plate which was dien vibrated with ultrasound, which caused the paste to penetrate and distribute evenly until all the fibre spaces were filled up. This was achieved during an ultrasound period of around 30 s.
  • the pasted electrode active area (pasted) dimensions were length 61 mm, width 44.7 mm, and thickness 2.22 mm.
  • the achieved lead loading per volume (pasted density of the electrode based on the mass loaded on to the electrode) was 1.402 g/ cm 3
  • active mass Pb to carbon volume ratio is 0.88.
  • the average spacing between carbon fibres was about 7 microns.
  • the electrode was air-dried for 24 hours at ambient temperature (18 °C— 24 °C) and then the pasted electrode was assembled in a cell containing electrolyte of 1.15sg H 2 S0 4 with one (40% SOC) positive electrode on each side. The cell was left soaking for 24 hours at ambient temperature ( 18 "C - 24 ll C). Then formation charging and stabilisation was carried out similarly to example 1.
  • Example 6 non-composite electrode of arc treated carbon felt, active mass/ carbon volume ratio ⁇ 2.63 - N356 - see figure 16 Method: An electrode was constructed of carbon fibrous layers of arc-treated carbon felt
  • the total amount of mass loaded in to the electrode was 15.60 g where the achieved capacity (low current discharging) was 1.93 Ah (i.e. 67% of the theoretical capacity).
  • the electrode active area (pasted) dimensions were, length 61.02 mm, width 44.77 mm, and thickness 2.34 mm.
  • the achieved lead loading per volume was 1.75 g/ cm 3 .
  • active mass Pb to carbon volume ratio is 2.63.
  • the average spacing between carbon fibres was about 37 microns.
  • the electrode was air-dried for 24 hours at ambient temperature ( 18 °C - 24 °C) and then the pasted electrode was assembled in a cell containing electrolyte of 1.15sg H 2 S0 4 with one (40% SOC) positive electrode on each side.
  • the cell was left soaking for 24 hours at ambient temperature ( 18 °C - 24 °C).
  • formation charging and stabilisation was carried out similarly to example 1.
  • An electrode was constructed of carbon fibrous layers of arc-treated carbon felt (Sigracell KFD2.5 EA manufactured by SGL Carbon Company, Germany).
  • the felt was treated in an electric arc generally as previously described with reference to Figures 7 and 8.
  • the felt before arc-treatment had a specific weight of 248 g/m 2 , thickness of 2.5 mm, and carbon volume fraction ⁇ 7 %.
  • the material post arc-treatment had 183 g/ m 2 specific weight, was 1.98 mm thick, and had ⁇ 6.6 % carbon volume fraction.
  • Lead coated copper wires of 0.38 mm in diameter were used as an additional current collector for the above electrode. These were laid on the felt surface manually along the length of the felt in a zig-zag manner so that the vertical strips were evenly spaced along the width prior to injecting the lug. The lug was injected onto the felt in a manner that the top (zag) of each line of the wire attached to the lug.
  • Preparation of paste and pasting was as described above for N363 except that an US time of 1 min 10 s was used.
  • the total amount of wet mass loaded in to the electrode was 17.79 g where the achieved capacity (low current discharging) was 2.03 Ah (i.e. 61% of the theoretical capacity).
  • the electrode active area (pasted) dimensions were, length 63.5 mm, width 44.85 mm, and thickness 2.71 mm.
  • the achieved lead loading per volume (pasted density of the electrode based on the mass loaded on to the electrode) was 1.66 g/ cm 3 . At the fully charged state of the electrode, active mass Pb to carbon volume ratio is 3.68.
  • the average spacing between carbon fibres was about 45 microns.
  • Tests and Results The cells were then transferred to test for standard cranking test at room temperature prior to sending for HR-DCAT testing. The results are set out in table 2 and figure 15.
  • An electrode was constructed of carbon fibrous layers of arc-treated carbon felt (Sigracell KFD2.5 EA manufactured by SGL Carbon Company, Germany).
  • the felt was treated in an electric arc generally as previously described with reference to Figures 7 and 8.
  • the felt before arc-treatment had a specific weight of 248 g/m 2 , thickness of 2.5 mm, and carbon volume fraction ⁇ 7.1 %.
  • the material post arc-treatment had 183 g/m 2 specific weight, was 1.98 mm thick, and had ⁇ 6.6 % carbon volume fraction.
  • the total amount of wet mass loaded in to the electrode was 17.66 g where the achieved capacity (low current discharging) was 2.11 Ah (i.e. 64.4% of the theoretical capacity).
  • the pasted electrode active area (pasted) dimensions were, length 61.71 mm, width 44.34 mm, and thickness 2.78 mm.
  • the achieved lead loading per volume was 1.67 g/ cm 3 .
  • active mass Pb to carbon volume ratio is 3.797.
  • the average spacing between carbon fibres was about 45 microns.
  • the electrode was air-dried for 24 hours at ambient temperature ( 18 °C - 24 °C) and then the pasted electrode was assembled in a cell containing electrolyte of 1.15 sg H 2 S0 4 with one (40% SOC) positive electrode on each side. The cell was left soaking for 24 hours at ambient temperature ( 18 °C - 24 °C). Then formation charging and stabilisation was carried out similarly to example 1.
  • Tests and Results The cells were transferred to submit them to standard cranking test at room temperature prior to sending for Axion-DCA testing.
  • Example 9 ⁇ non-composite electrode of arc treated carbon felt (thickness ⁇ 1.3mm) with an additional current collector of lead coated copper wires on felt surface ( approximately 1 m in total length), active mass/ carbon volume ratio ⁇ 4.893 - N441 - see figure 1
  • This electrode was constructed with carbon fibrous layers using arc-treated felt JX-PCF, manufactured by HeilongjiangJ&X Co., Ltd. China.
  • the felt had a specific weight of 508 g/m 2 , thickness of 4 mm and carbon volume fraction ⁇ 7.5 %.
  • the material was splitted in to a thinner strip (manually cutting using a sharp blade) and arc-treated as explained in previous examples.
  • Post arc-treatment had 144 g/m 2 specific weight, was 1.3 mm thick, and had ⁇ 6.4 % carbon volume fraction.
  • Lead coated Cu wires— 0.38 mm in diameter were used as an additional current collector for the above electrode.
  • the lug was prepared for this electrode in the same manner as explained in the example 5 above using solder ( 50% Sn and 50% Pb) making sure that top of each zag of the Cu wire was immersed in the lug and attached to the lug.
  • the total amount of wet mass loaded into the electrode was 16.11 g where the achieved capacity (low current discharging) was 2.052 Ah (i.e. 63% of the theoretical capacity).
  • the pasted electrode active area (pasted) dimensions were, length 59.8 mm, width 44.9 mm, and thickness 1.78 mm.
  • the achieved lead loading per volume (pasted density of the electrode based on the mass loaded into the electrode) was 2.64 g/ cm 3 . At the fully charged state of the electrode, active mass Pb to carbon volume ratio is 4.893.
  • the average spacing between carbon fibres was about 23 microns.
  • Example 10 non-composite electrode of arc treated carbon felt, active mass/carbon volume ratio ⁇ 2.53 - N387
  • An electrode was constructed of carbon fibrous layers of arc-treated carbon felt
  • the felt before arc-treatment had a specific weight of 248 g/ m 2 , thickness of 2.5 mm, and carbon
  • the material post arc-treatment had 203 g/ m 2 specific weight, was 2.25 mm thick, and had ⁇ 6.4 % carbon volume fraction.
  • the total amount of wet mass loaded in to the electrode was 14.2 g where the achieved capacity (low current discharging) was 1.68 Ah (i.e. 64% of the theoretical capacity).
  • Example 11 non-composite electrode of arc treated carbon felt, active mass/ carbon volume ratio ⁇ 2.696 - N392
  • An electrode was constructed of carbon fibrous layers of arc-treated carbon felt Sigracell KFD2.5 EA manufactured by SGL Carbon Company, Germany).
  • the felt was treated in an electric arc generally as previously described with reference to Figures 7 and 8.
  • the felt before arc-treatment had a specific weight of 248 g/m 2 , thickness of 2.5 mm, and carbon volume fraction ⁇ 7 %.
  • the material post arc-treatment had 203 g/m 2 specific weight, was 2.25 mm thick, and had ⁇ 6.4 % carbon volume fraction.
  • the total amount of wet mass loaded in to the electrode was 15.33 g where the achieved capacity (low current discharging) was 1.83 Ah (i.e. 64% of the theoretical capacity).
  • Example 12 amount of sulphuric acid used in paste
  • a small batch of paste made up of a suspension of particles of lead monoxide (97 mass %) and lead (3 %) together with water, and increasing amounts of acid were added.
  • the 3.0 g of solid was suspended in 3.65 g of water, achieving a solids mass fraction of 78 % and volume fraction of around 27 %. This was a freely settling slurry, difficult to keep uniformly suspended, and difficult to evenly spread onto a felt layer. Vibration (ultrasound) did not improve the properties and did not bring about easy penetration.
  • the pH of the liquid in equilibrium with the solids was 10. Small amounts of acid were added to bring the acid to around 0.12 mass % when a slight creaminess was observed, and the pH was around 9 to 9.5.

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Abstract

L'invention concerne une construction améliorée d'un accumulateur au plomb-acide. Des batteries comportent une construction d'électrode en fibre de carbone de l'invention et ont des valeurs de DCA et/ou de CCA améliorées, et/ou peuvent maintenir la valeur de DCA avec un nombre croissant de cycles de charge-de décharge, et peuvent ainsi être particulièrement adaptées à des fins d'utilisation dans des véhicules hybrides.
EP13757746.6A 2012-03-08 2013-03-08 Construction améliorée d'un accumulateur au plomb-acide Active EP2820702B1 (fr)

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